Process of making chlorinated bodies



Patented am. a, was.

UNHHD ears a asters ar ears aaice.

CARLETON ELLIS AND ALFRED A. WELLS, OF MONTGLAIR, NEW JERSEY, ASSIGNORS,

BY MESNE ASSIGNMENTS, T0 SETH B.

was.

HUNT, TRUSTEE, 0F MOUNT KISCQ, new

PROCESS OF MAKING CHLORINATED BODIES.

No Drawing.

bodies of an analogous character present inoii;

. derived from petroleum materialiand the like.

The raw material suitable for carrying out the present process may be found in large quantities in cracked gasoline or in the still gases or vapors from cracking stills I process is so-ca cracking heavy and other operations employed in the petroleum industry. A form of cracked gasoline which is suitable for the present lled Burton oil made by petroleum residues under a pressure of 75. lbs. or so. The lighter fractions boiling up to say 110-120 C. contain perhaps 10 to 20% of unsaturated bodies, a considerable portion of which are olefins adapted for use in the present process; These olefins may be extracted by treatment with sulphuric acid and halogenated to form the products described herein. In like manner other cracked products both light and heavy, depending upon the particular halogen product desired may be used. Olefins obtained from other sources such-as the natural olefins of shale oil or mineral oils of other kinds, also olefins obtained in various operations such as the production of Pinsch gas, Blau gas and the like or regenerated olefins obtained .in the sulphation other olefin material may be likewise employed. When products of comparatively low molecular weight are desired it is post sible-to utilize the still gases from petroleum which contain the vapors of unsaturated bodies. Gases obtained by. cracking petroleum in stills or in tubes may be collected and absorbed in sulphuric acid to give an acid extract suitable for making chlorinated or other form of halogenated bodies. In employing moist still gases it is important to dry these so that the sulphuric acid will not be diluted to a point where it will fail to absorb the gases freely.

United b process of making alcohols or Application filed April. 12, 1918. Serial'No. 228,128.

The acid preferably employed as indicated from the foregoing is sulphuric acid, ut any similarly acting acid may be used; especiall one of a dibasic or polybasic character. lxtures of selenic acid or phosphoric acid with sulfuric acid may be used, for example. Use of sulfuric acid is described herein. One difficulty which has heretofore been an obstacle in producing pure or fairly pure derivatives of etroleum has been tosecure a proper fractlon of the petroleum of the desired purit having the necessary reactive qualities. n a product as-complex as gasoline, for example Burton oil distillates, when a reaction produces products which great difficult would arise in their separation by disti lation or other methods. In the present case the sulphuric acid compound orproduct formed, which is herein termed acid extract or acid concentrate, separates with the greatest ease from the gasoline material so that simple settling or centrifugingenables the olefin acid extract to be obtained in a state of comparatively high purity almost wholly free from the great bulk of saturated hydrocarbon in which the olefins were initially dissolved or associated. Such a procedure thus enables a pure product, that is to say a product consisting mainly of olefins and sulphuric acid or the products of the reaction of'the acid on the olefins to be isolated in condition where it may be further treated for the production of chlorine-containing organic bodies. Likewise saturated hydrocarbons are isolated and may be used in the arts where qunsaturated hydrocarbons would be objectionable.

The production of the acid extract is an operation requiring considerable care in order to utilize the olefin material to good advantage. Some olefins readily polymerize in the presence of strong sulphuric acid pro-. ducing hydrocarbons, tars, resins and the like, which generally speaking are useless for the present purpose. While ethylene is quite stable in contact with strong sulphuric acid, and in fact apparently forms a compound therewith which' is stable even whenheated, the higher olefins polymerize or form tars quite quickly with strong sulphuric acid especially when the temperature is somewhat elevated. Accordingly in absorbing ethylene from still gases and the are miscible in the gasoline,

like the sulphuric acid may be heated and it may be strong, as for example 66 B. or 98% acid or even fuming acid. In handling still gases the higher olefins may be dissolved in diluted acid kept cool during the operation, as for example by vigorously .agl-

tating a quantity of sulphuric acid of 1.8 specific gravity kept at a temperature between and 20 C. while the acid is churned in contact with the gas, or by bub bling the gas therethrough. Under these conditions very little ethylene is dissolved and the gases leaving the first extractor may be passed into a second extractor Where there is present acid of 1.84 sp. gr. or higher and heated to 50 or 100 C. more or less. In this extractor the ethylene is absorbed to a considerable extent at least and the issuing gases largely depleted of their unbe mixed and chlorinated. The still gases may be treated in other ways; as for exampleby passing through towers containing sulphuric acid operating on the countercurrent system. In like manner the liquid gasoline obtained from cracking is agitated with the sulphuric acid, diluted acid or preferably acid of-1.8 specific gravity being run 1n a slow stream with cooling into a large body of .gasoline while agitating violently and allowing to settle, and collecting the extract which forms a fairly clearly defined layer on the bottom after standing for a brief eriod. (Jr the gasoline may be run into t e acid in some cases. If desired, the

extract may be blown with air or exposed to a vacuum to withdraw any loosely bound or entrained volatile hydrocarbons.

We have round that'it-is possible to directly chlorinate the acid extract produced by the sulphation treatment of the olefins. This sulphated material or acid extract may be treated as a chemical entity and may be subjected to halogenation in various ways to produce chlor or brom compounds and the like.

While the process herein described directly involves the production of petroleum derivatives containing halogen and more particularly chlorinated bodies, the invention, in certain of its aspects, covers'the recess of isolating hydrocarbons as well. Erasoline made by the cracking process contains relatively large quantities of unsaturea ers ated hydrocarbons. In ordinary refining processes it would not be feasible to take out these unsaturated bodies owing to'great shrinkage losses and-the cost? of the large amount of sulphuric acid required. Consequently itis the practice to treat asoline made in this way with sulphuric a id, say

derivatives which give a strong odor to the product and which also tend to discolor it. Thus gasoline is placed on the market containing from 5% and upwards of unsaturated bodies and these often give trouble due of the unsaturated bodies oxidize forming thick viscous compounds which are insoluble in the gasoline and separate causing considerable trouble. place in the carburetor of a gas engine much trouble ensues. As an extraction agent for removing fatty oils from seed. meal, etc., a saturated hydrocarbon solvent wliich does not leave a bad odor in the meal is desired. Unsaturated gasoline is not satisfactory for this purpose in many. cases. In dry cleaning, cleaning gloves, etc., a saturated hydrocarbon solvent which leaves no bad odor in the goods is greatly desired. Unsaturated compounds often leave an objectionable and very persistent odor. present rocess it is po ible to use a great excess 0? sulphuric acid i over what is ordinarily employed in refining and the unsaturated bodies may thus be largely or practically entirely removed if desired, furnishing on the one hand useful petroleum derivatives containing halogen and on the other hand.yielding-hydrocarbons which after refining may be said, from thestandpoint of degree of saturation, to quite closely approach Pennsylvania gasoline, which has been the standard of high quality due to its being com osed almost entirely of saturated bodies. n. the present process therefore after the extraction with sulphuric acid the gasoline may be collected and washed to remove free sulphuric acid and sulphonic compounds, etc., alkali being employed for the purpose. Material containing Mi -20% unsaturated bodies may havethc e reduced by the present process to but, a small percentage or practically none whatever, giving a sweet mixture of hydrocarbons acceptable as an extraction solvent. Ordinarily we do not reduce the content of unsaturated bodies below 2 or-3% as the remaining olefins are relatively stable.

.to the fact that on exposure to the air some When this action takes According to the While in the foregoing we have. mainly confined ourselves to olefins of a liquid character it should be distinctly understood that any olefin ranging tromethylene or propylone through the series maybe used an 'tract or concentrate.

tilled over.

eluding various Straight chain and branchin'g chain olefins, cyclic unsaturated hydrocarbons and all the other unsaturated bodies produced in cracking petroleum which react with sulphuric acid or other separating agent and chlorination'vehicle to enable the presentprocess to be carried out.

In one case a concentrated extract was made by saturating sulphuric acid of about 1.8 specific gravity with olefin material (B. P. 35-45" C.) obtained from cracked petroleum. This was treated with chlorine gas until the increase in weight was fully one-half the weight of the olefin taken. The temperature was not allowed to rise above 35 C. and under these conditions the reaction took place readily but not violently. There was no separation of chlorinated hydrocarbons from this mixture. When di luted with water and distilled a liquid heavier than water and insoluble therein dis- This was separated from the water and a portion was distilled. The initial boiling point was 120 C. and about two-thirds of the entire quantity of the material distilled over between 120 C. and 170 C. No odor of hydrochloric acid was perceptible during the distillation. The product burned with a flame having a green fringe. A portion was boiled-with strong caustic soda under a reflux condenser for one hour and after this treatment the ma terial had an alcoholic odor, although still containing some chlorine. in like manner the brominated compound may be obtained by the addition of bromine to the acid ex- Todine containing bodies may be produced by combination with iodine.

In another case olefin materialwas incorporated with sulphuric acid to form alkyl hydrogen sulphate or a solution containing the olefin in a substantially nonpolymerized state suitable as an acid extract or concentrate for chlorination purposes. The solution was diluted with water to ren-. der the strength of the sulphuric acid, it reckoned as such, approximately and any saturated or unsaturated hydrocarbons insoluble in the diluted extract were removed. The solution was placed in a receptacle surrounded by cold water and chlorine was passed in until enough chlorinehad been introduced in to produce a monochlor compound, calculating the mean molecular weight of the olefin material'on the basis of 5 carbon atoms. The treatment with'chlorine did not cause the acid concentrate to become heated to any material extent under these conditions. An equal volume of water was added and Jan immisciblelay r separated, which was distilled. This layer contained most of the chlorinated material although a small amount was still left in the diluted acid ex-l duce fluorine derivatives.

tract and was obtained by distilling the latter. Products havingthe following characteristics were obtalned:

Sp. gr.

In like manner a bromine or other halogenated product may be produced either fromacid. extract or concentrate obtained from gasoline or by the use of mixtures of olefins containing little or no unsaturated hydrocarbons.

The third method of treatment is that of preparing the acid extract and adding a salt of a halogen as sodium chloride or a bromide or iodide. The sodium, potassium, calcium, barium or other salts may be used. In one case the olefin was dissolved in sulphuric acid and sodium chloride added, no reaction being noticed until the'reaction liquid was heated to EEO-35. No odor of hydrohloric acid Was detected but rather an odor of sulphur dioxide. A chlorinated hydrocarbon insoluble in water was obtained together with a certain amount of polymerized hydrocarbon. Sodium or calcium fluoride may be used in like manner to,pro The acid extract employed may be either {concentrated or diluted when the salts are added. For an example with an olefin having one double bond the addition of, for example, sodium chloride, in an amount sufiicient to furnish one molecular weight of hydrochloric acid to a molecular weight of olefin is a satisfactory proportion to employ. With acid extract of unsaturated olefine material averaging five carbon atoms and containing about 4:9 parts of sulfuric acid, about 29' parts of sodium chloride will give substantially this molecular relation, although greater or lesser amounts may be used if desired. The temperature should be regulated to keep the reaction liquid cool or at least not at a temperature at which objectionable polymerization takes place rapidly. As the degree or case with which unsaturated hydrocarbons polymerize depends very largely on their structural. character and molecular weight, the conditions may be duly adjusted with reference to the particular material in hand. In like manner by chlorous acid or hypochlorites may be introduced into the acid extract. For example bleaching powder may be added to the acid extract with careful stirring and coolingto yield chlorinated compounds such as chlorhydrins and the like. In place of using salts such as sodium chloride, the free acid, such for example, as dry hydrochloric acid gas may be passed into the acid extract with agitation to bring about reaction.

-Thus there are obtained simple chl'o-ri nated hydrocarbons as for example from ethylene by treatment with chlorine an ethylene dichloride may be obtained While from propylene and butylene the corresponding chlorinated hydrocarbons are produced and thus from cracked gasolene new products are obtained, namely mixtures of chlorinated. hydrocarbons ordinarily corresponding to the olefins of cracked gasoline or of the unsaturated material of the particular raw hydrocarbons employed. Such correspondence is not wholly exact as some polymerizationor other changes may occur; but in general it may be stated that this invention especially aims to produce from an acid extract made with say propylene butylene and amylene, a mixture of chlorinated propylene, butylene and amylene. In carrying out the reaction ona large scale the apparatus may be cooled by a cooling jacket or by pipes through which the water or I brine is passed, at least during that stage when considerable heat is evolved.

The concentration or degree of dilution of the acid extract my vary considerably depending on whether or not chlor compounds such as chlorethane or dichlorethane, monochlor propane and the like are desired or whether chlorhydrins are to be produced as the more diluted the extract the greater the ease with which chlorhydrins may be expected to be formed, other conditions being equal. Thus the process comprises chlorinating unsaturated aliphatic hydrocarbons in a sulphuric acid vehicle or more broadly in halogenating under such conditions. Whether or not the unsaturated material forms a definite compound with the sulphuric acid or merely a solution, is not an essential consideration herein, the product obtained with sulphuric acid being treated with chlorine or other halogen, or compoundthereof, to yield suitable halogenated products, which may be separatedfrom the sulphuric acid and purified as halogen derivatives of said unsaturated material.

What we claim is 1. The process of making chlorinated hy droc'arbons or other chlorinated bodies which comprises subjecting acid extract to the which comprises subjecting acid extract to the action of a halogenated agent.

4. The process of making halogenated products from the unsaturated hydrocarbons of gasoline which comprises extracting gasoline containing unsaturated bodies with an' M extracting agent comprlslng sulphuric acidof a strength corresponding to about 1.8 specific gravity whereby an acid extract is formed and in reacting on said acid extract with a halogen-introducin' agent.

5. The process of ma ing halogenated products from the unsaturated hydrocarbons of gasoline which comprises extracting gasproducts from the unsaturated hydrocarbons of gasoline which comprises extracting gas- ,a n A oline contalning unsaturated bodies with an extracting agent comprising sulphuric acid of a strength corresponding to about 1.8 specific gravity, whereby an acid extract is formed and in reacting on said acid extract withchlorine.

7. The process of making chlorinated products from the unsaturated hydrocarbons of gasoline which comprises extracting gasoline containing unsaturated bodies with an extracting agent comprising sulphuric acid whereby an acid extract is formed and in reacting on said extract with chlorine.

8. The process of making halogenated products from the unsaturated hydrocarbons of gasoline which comprises treating gasoline containing olefin material with sulphuric acid of a strength corresponding to about 1.8 specific gravity, whereby an acid solution is formed and in reacting on said acid solution with a halogen-introducing agent.

9. The process of making halogenated products from olefine hydrocarbons which comprises extracting liquids containing olefine hydrocarbons with sulfuric acid whereby a'reactive acid extract is formed, and in reacting on said acid extract wit-h a halogen-introducing agent.

10. The process of making chlorinated hydrocarbons which comprises exposingacid extract to chlorine gas and withdrawing the heat of reaction.

11. The process of making chlorinated bodies which comprises exposing diluted acid extract of an acid strength correspond ing to about 1.7 specific gravity to the action of chlorine.

12. The process of making chlorinated derivatives of hydrocarbons, which comprises adding water to acid extract and exposing it to the action of a chlorinating agent. f

13. The process of making halogenated derivatives of hydrodarbons, which comprises adding water to acid extract and exposing it to the action of a haloge nating agent.

14. a mixture of chlorinated hydrocarbons substantially from saturated hydrocarbons and As a new article of manufacture,-

derived from olefines of cracked petroleum by sulfation of said olefines to form a reactive acid extract followed by chlorination of the acid extract.

15. As a new article of manufacture, a mixture of halogenated hydrocarbons, substantially free from saturated hydrocarbons derived from olefines of cracked petroleum by sulfation of said olefines to form areactive acid extract, separation of the reactive acid extract from saturated hydrocarbons, and halogenation of the said extract. 16. The process of halogenation which principally of the olefine type in a sulphuric acid Vehicle.

' CARLETON ELLIS,

ALFRED A. WELLS. 

